Graphene oxide quantum dots embedded polysulfone membranes with enhanced hydrophilicity, permeability and antifouling performance

  • Guoke Zhao (赵国珂)
  • Ruirui Hu (胡蕊蕊)
  • Jing Li (李晶)
  • Hongwei Zhu (朱宏伟)Email author


Graphene oxide (GO) has been demonstrated to be an effective hydrophilic nanofiller to modify the polymeric membranes when forming a mixed matrix structure. GO quantum dots (QDs) are promising candidates to fully exert the rich oxygen containing functional groups due to their unique size induced edge effects. In this work, GO QDs modified polysulfone (PSF) ultrafiltration (UF) membranes were prepared by phase inversion method with various GO QDs loadings (0.1–0.5 wt.%). A proper amount of GO QDs addition led to a more porous and hydrophilic membrane structure. With 0.3 wt.% GO QDs, the membranes showed a 60% increase in permeability (130.54 vs. 82.52 LMH bar−1). The pristine PSF membranes had a complete cutoff of bovine serum albumin molecules and it was well maintained with GO QDs incorporated. The membranes with 0.5 wt.% GO QDs exhibited the highest flux recovery ratio of 89.7% and the lowest irreversible fouling of 10.3% (54.5% and 33.3% for the pristine PSF membranes). Our results proved that GO QDs can function as effective nanofillers to enhance the hydrophilicity, permeability and antifouling performance of PSF UF membranes.


graphene oxide quantum dots ultrafiltration membrane antifouling 



氧化石墨烯(GO)是一种有效的对高分子膜进行添加改性的亲 水性纳米材料, 氧化石墨烯量子点(GO QDs)在保持GO结构的同时, 其小尺寸所致的边缘效应, 使其具有更加丰富的含氧官能团. 本文采 用相转化法制备了GO QDs改性的聚砜超滤膜, 合适添加量的GO QDs提高了复合膜的孔隙率和亲水性. 当GO QDs添加量为0.3 wt.% 时, 复合膜的水通量提高了60%(130.54 vs. 82.52 LMH bar−1), 并实 现了对牛血清白蛋白分子的完全截留. 在抗污染测试中, GO QDs 添加量为0.5 wt.%的复合膜具有最高的通量回复率(89.7%)和最低 的不可逆污染率(10.3%). 该研究表明GO QDs作为添加改性材料, 可有效提高聚砜超滤膜的亲水性、水通量和抗污染性能.



This work was supported by Beijing Natural Science Foundation (2172027).

Supplementary material

40843_2019_9417_MOESM1_ESM.pdf (357 kb)
Supplementary material, approximately 228 KB.


  1. 1.
    Shannon MA, Bohn PW, Elimelech M, et al. Science and technology for water purification in the coming decades. Nature, 2008, 452: 301–310CrossRefGoogle Scholar
  2. 2.
    Oki T, Kanae S. Global hydrological cycles and world water resources. Science, 2006, 313: 1068–1072CrossRefGoogle Scholar
  3. 3.
    Shaffer DL, Arias Chavez LH, Ben-Sasson M, et al. Desalination and reuse of high-salinity shale gas produced water: drivers, technologies, and future directions. Environ Sci Technol, 2013, 47: 9569–9583CrossRefGoogle Scholar
  4. 4.
    Lee CW, Bae SD, Han SW, et al. Application of ultrafiltration hybrid membrane processes for reuse of secondary effluent. Desalination, 2007, 202: 239–246CrossRefGoogle Scholar
  5. 5.
    Afonso MD, Bórquez R. Review of the treatment of seafood processing wastewaters and recovery of proteins therein by membrane separation processes—prospects of the ultrafiltration of waste-waters from the fish meal industry. Desalination, 2002, 142: 29–45CrossRefGoogle Scholar
  6. 6.
    Chung YT, Mahmoudi E, Mohammad AW, et al. Development of polysulfone-nanohybrid membranes using ZnO-GO composite for enhanced antifouling and antibacterial control. Desalination, 2017, 402: 123–132CrossRefGoogle Scholar
  7. 7.
    Gao W, Liang H, Ma J, et al. Membrane fouling control in ultrafiltration technology for drinking water production: A review. Desalination, 2011, 272: 1–8CrossRefGoogle Scholar
  8. 8.
    Shi X, Tal G, Hankins NP, et al. Fouling and cleaning of ultrafiltration membranes: A review. J Water Process Eng, 2014, 1: 121–138CrossRefGoogle Scholar
  9. 9.
    Otitoju TA, Ahmad AL, Ooi BS. Recent advances in hydrophilic modification and performance of polyethersulfone (PES) membranevia additive blending. RSC Adv, 2018, 8: 22710–22728CrossRefGoogle Scholar
  10. 10.
    Chan R, Chen V. Characterization of protein fouling on membranes: opportunities and challenges. J Membrane Sci, 2004, 242: 169–188CrossRefGoogle Scholar
  11. 11.
    Jhaveri JH, Murthy ZVP. A comprehensive review on anti-fouling nanocomposite membranes for pressure driven membrane separation processes. Desalination, 2016, 379: 137–154CrossRefGoogle Scholar
  12. 12.
    Miller DJ, Dreyer DR, Bielawski CW, et al. Surface modification of water purification membranes. Angew Chem Int Ed, 2017, 56: 4662–4711CrossRefGoogle Scholar
  13. 13.
    Grace JM, Gerenser LJ. Plasma treatment of polymers. J Dispersion Sci Tech, 2007, 24: 305–341CrossRefGoogle Scholar
  14. 14.
    Wang H, Wang W, Wang L, et al. Enhancement of hydrophilicity and the resistance for irreversible fouling of polysulfone (PSF) membrane immobilized with graphene oxide (GO) through chloromethylated and quaternized reaction. Chem Eng J, 2018, 334: 2068–2078CrossRefGoogle Scholar
  15. 15.
    Lee J, Chae HR, Won YJ, et al. Graphene oxide nanoplatelets composite membrane with hydrophilic and antifouling properties for wastewater treatment. J Membrane Sci, 2013, 448: 223–230CrossRefGoogle Scholar
  16. 16.
    Kumar M, Gholamvand Z, Morrissey A, et al. Preparation and characterization of low fouling novel hybrid ultrafiltration membranes based on the blends of GO-TiO2 nanocomposite and polysulfone for humic acid removal. J Membrane Sci, 2016, 506: 38–49CrossRefGoogle Scholar
  17. 17.
    Wu H, Tang B, Wu P. Development of novel SiO2-GO nanohybrid/polysulfone membrane with enhanced performance. J Membrane Sci, 2014, 451: 94–102CrossRefGoogle Scholar
  18. 18.
    Yan L, Li Y, Xiang C, et al. Effect of nano-sized Al2O3-particle addition on PVDF ultrafiltration membrane performance. J Membrane Sci, 2006, 276: 162–167CrossRefGoogle Scholar
  19. 19.
    Bottino A, Capannelli G, Comite A. Preparation and characterization of novel porous PVDF-ZrO2 composite membranes. Desalination, 2002, 146: 35–40CrossRefGoogle Scholar
  20. 20.
    Huang ZQ, Zheng F, Zhang Z, et al. The performance of the PVDF-Fe3O4 ultrafiltration membrane and the effect of a parallel magnetic field used during the membrane formation. Desalination, 2012, 292: 64–72CrossRefGoogle Scholar
  21. 21.
    Ng LY, Mohammad AW, Leo CP, et al. Polymeric membranes incorporated with metal/metal oxide nanoparticles: A comprehensive review. Desalination, 2013, 308: 15–33CrossRefGoogle Scholar
  22. 22.
    Sun P, Wang K, Zhu H. Recent developments in graphene-based membranes: structure, mass-transport mechanism and potential applications. Adv Mater, 2016, 28: 2287–2310CrossRefGoogle Scholar
  23. 23.
    Huang H, Ying Y, Peng X. Graphene oxide nanosheet: an emerging star material for novel separation membranes. J Mater Chem A, 2014, 2: 13772–13782CrossRefGoogle Scholar
  24. 24.
    Gopinadhan K, Hu S, Esfandiar A, et al. Complete steric exclusion of ions and proton transport through confined monolayer water. Science, 2019, 363: 145–148CrossRefGoogle Scholar
  25. 25.
    You Y, Jin XH, Wen XY, et al. Application of graphene oxide membranes for removal of natural organic matter from water. Carbon, 2018, 129: 415–419CrossRefGoogle Scholar
  26. 26.
    Nair RR, Wu HA, Jayaram PN, et al. Unimpeded permeation of water through helium-leak-tight graphene-based membranes. Science, 2012, 335: 442–444CrossRefGoogle Scholar
  27. 27.
    Lian B, De Luca S, You Y, et al. Extraordinary water adsorption characteristics of graphene oxide. Chem Sci, 2018, 9: 5106–5111CrossRefGoogle Scholar
  28. 28.
    Lv J, Zhang G, Zhang H, et al. Graphene oxide-cellulose nanocrystal (GO-CNC) composite functionalized PVDF membrane with improved antifouling performance in MBR: Behavior and mechanism. Chem Eng J, 2018, 352: 765–773CrossRefGoogle Scholar
  29. 29.
    Hegab HM, Zou L. Graphene oxide-assisted membranes: Fabrication and potential applications in desalination and water purification. J Membrane Sci, 2015, 484: 95–106CrossRefGoogle Scholar
  30. 30.
    Zhao G, Li X, Huang M, et al. The physics and chemistry of graphene-on-surfaces. Chem Soc Rev, 2017, 46: 4417–4449CrossRefGoogle Scholar
  31. 31.
    Zhao H, Wu L, Zhou Z, et al. Improving the antifouling property of polysulfone ultrafiltration membrane by incorporation of isocyanate-treated graphene oxide. Phys Chem Chem Phys, 2013, 15: 9084–9092CrossRefGoogle Scholar
  32. 32.
    Zambare RS, Dhopte KB, Patwardhan AV, et al. Polyamine functionalized graphene oxide polysulfone mixed matrix membranes with improved hydrophilicity and anti-fouling properties. Desalination, 2017, 403: 24–35CrossRefGoogle Scholar
  33. 33.
    Xu ZW, Zhang J, Shan M, et al. Organosilane-functionalized graphene oxide for enhanced antifouling and mechanical properties of polyvinylidene fluoride ultrafiltration membranes. J Membrane Sci, 2014, 458: 1–13CrossRefGoogle Scholar
  34. 34.
    Safarpour M, Vatanpour V, Khataee A. Preparation and characterization of graphene oxide/TiO2 blended PES nanofiltration membrane with improved antifouling and separation performance. Desalination, 2016, 393: 65–78CrossRefGoogle Scholar
  35. 35.
    Zheng XT, Ananthanarayanan A, Luo KQ, et al. Glowing graphene quantum dots and carbon dots: properties, syntheses, and biological applications. Small, 2015, 11: 1620–1636CrossRefGoogle Scholar
  36. 36.
    Li Y, Zhao Y, Cheng H, et al. Nitrogen-doped graphene quantum dots with oxygen-rich functional groups. J Am Chem Soc, 2012, 134: 15–18CrossRefGoogle Scholar
  37. 37.
    Song X, Zhou Q, Zhang T, et al. Pressure-assisted preparation of graphene oxide quantum dot-incorporated reverse osmosis membranes: antifouling and chlorine resistance potentials. J Mater Chem A, 2016, 4: 16896–16905CrossRefGoogle Scholar
  38. 38.
    Fathizadeh M, Tien HN, Khivantsev K, et al. Polyamide/nitrogen-doped graphene oxide quantum dots (N-GOQD) thin film nanocomposite reverse osmosis membranes for high flux desalination. Desalination, 2019, 451: 125–132CrossRefGoogle Scholar
  39. 39.
    Bi R, Zhang Q, Zhang R, et al. Thin film nanocomposite membranes incorporated with graphene quantum dots for high flux and antifouling property. J Membrane Sci, 2018, 553: 17–24CrossRefGoogle Scholar
  40. 40.
    Xu S, Li F, Su B, et al. Novel graphene quantum dots (GQDs)-incorporated thin film composite (TFC) membranes for forward osmosis (FO) desalination. Desalination, 2019, 451: 219–230CrossRefGoogle Scholar
  41. 41.
    Wang M, Pan F, Yang L, et al. Graphene oxide quantum dots incorporated nanocomposite membranes with high water flux for pervaporative dehydration. J Membrane Sci, 2018, 563: 903–913CrossRefGoogle Scholar
  42. 42.
    Wang H, Lu X, Lu X, et al. Improved surface hydrophilicity and antifouling property of polysulfone ultrafiltration membrane with poly(ethylene glycol) methyl ether methacrylate grafted graphene oxide nanofillers. Appl Surf Sci, 2017, 425: 603–613CrossRefGoogle Scholar

Copyright information

© Science China Press and Springer-Verlag GmbH Germany, part of Springer Nature 2019

Authors and Affiliations

  • Guoke Zhao (赵国珂)
    • 1
  • Ruirui Hu (胡蕊蕊)
    • 1
  • Jing Li (李晶)
    • 1
  • Hongwei Zhu (朱宏伟)
    • 1
    Email author
  1. 1.State Key Lab of New Ceramics and Fine Processing, School of Materials Science and EngineeringTsinghua UniversityBeijingChina

Personalised recommendations